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By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world's largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By J. W. Pamplin

SOME 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.' Physically the phosphate-bearing formation, locally called the “matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca3P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by ½ mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, some- times a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the “hydraulic line." This 700 yd. of overburden and 300 yd. of matrix-1000 yd. in all- amounts to about 1500 tons of material moved each hour. The over- burden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7 ½ long tons in 4000 gal. of water per minute-a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

"Salt Lake City was founded July 24, 1847, by Mormons under the leadership of Brigham Young. It had a population of 118,110, according to the United States census of 1920, and of 151,968, according to a civic survey, January 1, 1925. The Salt Lake metropolitan district is estimated to have 180,079 inhabitants.The city's area is 51.8 square miles. Its altitude is 4,354 feet. It has 514 miles of streets, of which 91 miles are paved. The streets in the main portion of the city are 132 feet wide and the blocks are 660 feet long. It has 144 miles of street railway and 2,200 electric street lights. It has fifteen parks and playgrounds, forty public schools and six private schools. It has eighty-nine church edifices, of which forty-nine are devoted to denominations other than the Mormon Church.It is the capital of the state, the headquarters of the Mormon Church and the headquarters of most of the mining companies and many other business institutions of the state and adjacent territory.The State University, the State School of Mines and the Inter-Mountain Experiment Station of the U. S. Bureau of Mines are in the eastern part of the city. Fort Douglas is east of the University the country clubs are in the southeastern portion of the city. The State Fair Grounds are in the northwestern portion.The city is the center of a trade area about 700 miles in diameter and is in almost the exact center of a circle that embraces the principal western mining areas. It is the home of several widely-known mining supply companies and all the other leading concerns in that line are represented by agency or branch house."

Jan 1, 1925

By B. S. Hickman

Using primarily quantitative single crystal X-ray techniques studies have been made of the precipitation of the metastable w phase in alloys of titanium with Mo, Mn, Fe, Cr, and Nb. It is shown that, in agreement with earlier work on the Ti-V system, the composition of the w phase during aging approaches a constant; the value varies from one system to another in a systematic manner with the electron concentmtion. Results relevant to the mechanism of w precipitation during quenching and during aging are presented and discussed. Results are presented to confirm that the w phase is coherent and the nzorphology of the Necipitates is described and discussed. PRECIPITATION of the metastable w phase in alloys of titanium is of interest because of its severe embrittling effect and also because of the enhancement of the superconducting properties which accompanies precipitation.1 The general features of w phase precipitation have been discussed by cuillan and by Bagaratskii et d3 The work described in this paper forms part of a general study of w phase precipitation which was undertaken to elucidate various unknown or controversial features of the process, namely: i) What is the mechanism of formation of the phase ii) How does its composition, morphology, volume fraction, and particle size vary with the type and content of the alloying element and with the heat treatment conditions? iii) What is the relation between the w phase and the equilibrium a phase? In a previous paper4 the results of a detailed study of w phase in Ti-V alloys were presented. It was shown that: U During aging the composition of the w phase approached a saturation value of 13.5 to 14.0 at. pct V. ii) w precipitated as cube shaped particles and once precipitation was complete, particle coarsening did not occur. iii) a phase formed initially by direct conversion of w-phase precipitates. In this paper similar measurements are reported on Ti-Mo alloys and some more limited data given on the Ti-Cr, Ti-Fe, Ti-Mn, and Ti-Nb systems. The results i.1 the six systems are then compared. It has been shown previously by electron microscopy that the w precipitates as ellipsoids in both the Ti-Nb system,&apos; and in i-o.&apos; Blackburn and williamsz3 have reported the precipitates in Ti-Fe, Ti-Cr, and Ti-Mn are cubic, i.e., similar to the Ti-V system.476 EXPERIMENTAL METHODS 1) Specimen Preparation. Samples of the compositions shown in Table I were prepared by arc melting. High purity electron beam zone refined titanium (Materials Research Corporation Grade I—total impurity content =250 ppm) was used; the other source materials are given in the table. A commercial Ti-8 wt pct Mn alloy was used for studies of this system. After homogenization the materials were rolled or cut into strip approximately 1/4 in. by 2 in.; the strip was then heated at temperatures of 1200" to 1300°C for several hours by passage of a direct current through the strip in an ultra high vacuum system (<10-torr) and then quenched by admitting high purity helium and switching off the current. This treatment resulted in crystals up to 2 in. by 2 in. by A in., almost all of which had a [100] direction nearly perpendicular to the plane of the strip. The crystals were cut from the strip by spark machining and their composition checked by lattice parameter measurements supported by chemical analysis. 2) X-Ray Diffraction Methods. Lattice parameter measurements were made using a modification of the single crystal spectrometer described by ond. In this technique the crystal angles for reflection on either side of a highly collimated primary beam are measured. Generally the 400 CuK, or the 400 CuKp reflections of the bcc lattice were used. In the as-quenched crystals a precision of 1 in 105 was obtained, but due to line broadening the parameters in aged materials could only be measured to 1 in lo4. This accuracy was, however, quite adequate for the purposes of these experiments and enabled the composition of the p phase to be obtained to 10.1 pct in all systems except Ti-Nb where the lattice parameter change with composition is very small. The precipitation and growth of the w phase was examined using a single crystal goniometer attached to a Phillips diffractometer. The relative intensities and line shapes of b-phase and w-phase reflections

Jan 1, 1970

By Patrick H. O’Neill

The Choco placers, mined continuously since the earliest expeditions of the Spanish conquistadors, were exploited by the Indians prior to the conquest. Platinum is found in varying percentages with gold throughout the Choco placers and is found in minor percentages in some placers in other parts of Colombia. The Choco Department is on the west coast of Colombia between the western range of the Andes and the Pacific Ocean and extends from the San Juan River north beyond Panama to the Caribbean. The first reference in European literature to platinum was by Julius Caesar Scaliger in 1557. He did not assign any name to it but referred to it as an infusible metal found in the mines in the New World. The Spaniards had given it the name platina, which is the diminutive for plata, the Spanish word for silver. Don Antonio de Ulloa first recorded the name while on an official visit to the Choco from Spain in 1735.

May 1, 1956

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926

By O. C. Ralston, William C. Hunter

DUring experimental study on the separation of a zinc concentrate from the heavy sulfide ores of Jerome, Ariz., a great deal of attention has been given to proper activation of the sphalerite content of the ore. The sphalerite at Jerome contains enough iron to class it as a marmatite, as picked specimens have only about 60 per cent. zinc, whereas pure zinc sulfide contains 67 per cent. zinc. This marmatite in large pieces is black in color, but in dry powdered state is brown. A flotation froth made from it has a silvery black luster in comparison with a brassy luster caused by chalcopyrite which occurs in the same ores. The sample used in most of the experiments described below consisted of about 3000 Ib. of diamond-drill core from the zinc-bearing orebodies of the United Verde mine, and had the following analysis: Per Cent. Per Cent. Oz. peR Ton Cu............... 0.695 Al2O3............ 0.83 Ag................. 1.30 Zn............... 6.17 S................ 43.35 Au................ 0.02 Fe...............36.23 CaO............. 0.46 SiO2............. 9.27 Mineralogically, this analysis is calculated to the following, which is in agreement with the microscopic examination: Per Cent. Per Cent. Chalcopyrite................... 2.0 Schist........................... 3.2 Marmatite..................... 10.32 Quartz........................... 8.2 Pyrite........................ 73.0 Calcite.......................... 0.9 All samples were ground in a laboratory ball mill in order to leave about 3 per cent. on a 200-mesh sieve, fine grinding being essential to liberate the minerals in the ore. Most of the Jerome ores are so intimately crystallized that reasonably complete unlocking by grinding does not take place until 800 mesh is approached. Therefore, the 200-mesh grind adopted contains a considerable amount of locked mineral grains, but not so much as to render impossible the preparation of commercial grades of concentrate.

Jan 1, 1930

By C. H. Gerould

I would like to take a moment to consider our polystyrene-silica replica technique, which was developed at the Dow Chemical Co. and which was mentioned in the paper just given by Mr. Thielsch. He stated that he feared that our replica technique would cause difficulty due to deformation of the metal as a result of the application of pressure during the molding process. We at the Dow have never had any reason to suspect that any deformation of the metal was occurring during the molding process. Our procedure has been to heat the polystyrene to a temperature of 160°C. before applying any pressure, at which temperature the polystyrene is a viscous liquid. By so doing the pressure of the polystyrene against the metal is essentially hydraulic and is therefore applied equally in all directions, which we feel should not cause deformation. Our work using this replica technique has brought forth several indications that deformation of the specimen is negligible. These indications are: I. Direct comparisons have been made between the light and electron microscopes when studying a specific spot on a metal surface. These "same spot" studies were obtained by first taking micrographs at high magnification, with a light microscope, of a specific structure that could be readily recog-

Jan 1, 1947

By Thomas Watson

INTRODUCTION THE users of barite in the United States derive their supply partly from the domestic production and partly from the imports from foreign countries. According to the Mineral Resource division of the U. S. Geological Survey, the domestic production of barite in 1913 was 45,298 short tons, valued at $156,275, or $3.45 a ton, and the imports of crude barite were 35,840 short tons, valued at $61,409, or $1.71 a ton. These figures clearly show a decided advantage in cost of the foreign over the domestic barite to users in the United States. The difference in cost is the only advantage to the consumer of foreign barite, for there are large reserves of the mineral in the United States of good grade. The production of many of the operating mines is capable of decided increase, and it is believed that the operating mines together with the large reserves of undeveloped deposits of barite are entirely adequate to meet the demands of the users in the United States. Deposits of barite are known in California, Idaho, Nevada, and Alaska, but most of them are undeveloped because there is, apparently, no market for the .material in that region. The domestic production is derived from Missouri and the Appalachian States, the greater part being obtained from Missouri. Following the outbreak of war in Europe many users of foreign barite in the United States have been forced to seek their supplies at home. It seems opportune at this time, therefore, that a general review be given of the barite industry in the Appalachian States, one of the two areas from which the domestic supply of the mineral is derived, and that attention be directed to the undeveloped deposits in the region. Briefly, then, this paper reviews the barite industry in the Appalachian States, and describes the occurrence, preparation, and uses of the mineral.

Jan 2, 1915

By William P. Blake

In another paper I have described in general the close association of zinc-blende and iron pyrites in the ore-deposits of southwest Wis consin. These two minerals generally occur together at the same horizon, a sheet of one being overlain by a sheet of the other; and also the pyrites is disseminated through the blende to such a degree that the latter is rendered comparatively worthless for the produc tion of spelter. Ordinarily the pyrites, which is mostly the trimetric marcasite variety, occurs in about equal quantity with the blende and is separated by hand-culliug and chipping; but there are large de posits where the ores are so closely mixed that they can neither be separated by culling nor by any mechanical method. The specific gravity of the two minerals is so nearly the same that attempts often made to effect even a partial separation by jigging have proved un. successful. The smelters of zinc-ores in the Mississippi valley will not take ores which carry more than 7 per cent. of iron; and it is therefore necessary to cull the massive (&apos;jack" with great care and at consid erable expense, in order to bring it up to the market-standard of purity. The results of trials to effect a separation of blende and pyrites in other regions have been equally unsatisfactory. The literature of this branch of metallurgy abounds in examples. In Wisconsin efforts have been made in the past to " burn " the mixed ores in heaps, in order to soften or destroy the pyrites, and facilitate its separation from the massive blende. The same method has also been resorted to when galenite is mixed through the substance of the blende, for the purpose of disintegrating the ore, so that it could be separated by jigging. The custom was to pile the ore and the fuel together. As might have been expected, the results were far from satisfactory. As is usual in heap-roast ing, some portions of the ore were overheated and decomposed; zinc was lost by volatilization; the galenite in some portions was

Jan 1, 1894

US Tin Mission To Study Costs in Far East A move to obtain adequate supplies of tin at prices the United States is willing to pay was initiated when the interagency tin mission left for the Far East. The Mission, which includes representatives of the Reconstruction Finance Corporation, State Department, Defense Minerals Procurement Agency and the Bureau of Mines will go to Indonesia and Malaya. The primary purpose of the mission, according to officials, will be to study tin production costs, not to negotiate for the purchase of tin. The mission will be prepared to enter into negotiations, if the Far Eastern producers are amenable. The United States withdrew as a large-scale buyer of tin some months ago in protest against what it considered exorbitant prices being charged in the Singapore market. Subsequent attempts to negotiate for a steady tin supply at what this country considers reasonable prices have been unavailing. The U. S. is prepared to enter into a two or three year contract with the price of tin somewhere between $1.00 to $1.12 per lb. The decision to abstain from the market has not yet put a squeeze on U. S. supplies. Substantial quantities of tin still are coming in from Malaya under an old contract.

Jan 12, 1951

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By Clinton M. Young

The experiments herein described were carried on in 1908-9 by- the State Geological Survey of Kansas. Some months before taking up work on black powder the Survey had resumed work on an interrupted investigation of explosions in coalmines, a subject which is engaging the attention of numerous investigators. An unusual number of serious disasters has directed to the subject a study which discloses the disquieting fact that, in the United States, the ratio of lives lost per ton of coal mined has been 011 the increase. Methods of coal-mining have changed to some extent with the great increase of output, attained in comparatively recent years. These changes involve the working of very extensive mines, with increased difficulty of ventilation, increased accumulation of coal-dust, and a very great increase in the amount of explosive used. This last point assumes truly startling proportions when it is carefully observed. In the fields of the Middle West it is not now uncommon for a miner to use six kegs (150 lb.) of black powder in a " pay" of two weeks, while within the memory of men still active, one keg (25 Ib.) would last two men for a " pay." So great has the use of explosives become in some fields that the skilled coal-miner is hard to find, and the coal is not mined, but blasted. A preliminary study of the subject of explosions in coalmines has led to the belief that the use of large quantities of explosives, in some cases by slightly-trained men, had riot been

Jan 1, 1911

By F. Peter

I. GENERAL INTRODUCTION. TECHNICAL progress takes place in two directions: the improvement of methods, affecting the quality of the product; and increase in the economy of operations, affecting its cost. In the iron-industry, practice is pretty well settled, and. revolutionary changes of method are, for the present, not to be expected. Hence, in this industry, the principal endeavor is to reduce costs by the use of labor-saving inventions, such as the machines brought into use during the last decade. But it is not alone necessary to reduce the labor-cost; complete economy requires also a saving in raw material. Under this head we may rank the coal employed as metallurgical fuel; and it follows that progress includes the economic use of fuel, so managed as not to injure quality of product. In the present paper it will be shown how, by suitable utilization of the heat from the furnace, a large portion of it may be made available for other purposes. Such utilization of waste-gases is important in all industries which employ furnaces (especially heating- and smelting-furnaces); and in the first rank of these stand the iron-, glass-, and porcelain-manufactures. The following pages are devoted chiefly to the waste-gases of smelting-works, and especially to those reverberatory-furnace gases which are not combustible.&apos;

Jan 12, 1913

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

INTRODUCTION Data available on prophyry copper occurrences in the Andean, Caribbean, Appalachian, and Cordilleran orogens may be categorized in a manner to suggest a hypothetical evolution for deposits that occur in the western hemisphere. A classification of de- posits is also suggested. A classification dependent on internal structure of a porphyry copper deposit would lead to two broad categories, breccia pipe and stockwork models. A classification of this type is examined herein but it is not universally accepted in the literature. Modeling based on igneous petrography as well as metasomatism attendant with the sulfide mineralization is more widely accepted by economic geologists whose evaluation of porphyry systems is influenced by the presence or absence of a phyllic zone. Lowell and Guilbert model deposits ordinarily include a phyllic zone, whereas those of the diorite model do not. Position of the phyllic zone in the alteration sequence is a significant ore guide. Should the phyllic zone be absent, dependence on alteration zoning to identify metallization is weakened. Presence or absence of the phyllic zone therefore is a significant parameter in the economic evaluation of a porphyry copper deposit (Hollister. et al., 1975). The Lowell and Guilbert (1970) model commonly includes a phyllic zone in quartz- bearing rocks. Parameters of both calc-alkalic and the quartz monzonite models mentioned elsewhere in this volume are sufficiently close to the Lowell and Guilbert (1970) model that it should be expanded to encompass them. The diorite model remains separate and distinct because deposits of this type are characterized by an absence of quartz in the pluton, commonly highly gold: copper ratios, low molybdenum content, and regular absence of sericite in the alteration zones. Therefore, for the benefit of those

Jan 1, 1978

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre- Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining counties cover most of the highly mineralized section of the Front Range which extends from James- town to Breckenridge. As far as the writer is aware, uranium has been found only in the portion north-east of Lawson.

Jan 1, 1950

By H. M. Chance

In the early part of 1893, I had occasion to make for the owners a professional examination of the Rich Patch tract; and, with their permission, I present in this paper, omitting the commercial portions of my report, those portions which may be valuable to future students of that region. Location, Topography And Geology. The Rich Patch tract comprises about 9000 acres, located about 3 miles west of Low Moor, on the Chesapeake and Ohio Railway, in Alleghany county, Va., and immediately adjoining the Low Moor property. In shape the tract is roughly quadrangular, being about 3 miles broad in a northerly and southerly direction, by about 6 miles long from east to West. Potts creek and Jackson river run along its northern boundary. It is drained by Hayes Gap run, Mill branch and Laurel creek, which flour north into Potts creek, and by Karnes creek, which flows northeasterly through the Low Moor property into Jackson river. The topography of the tract is shown by the accompanying map (Fig. I), and need not be described here. The valleys are cut down from 1000 to 1500 feet below the mountain summits, which generally reach an altitude of about 3000 feet above tide. The geological structure of the district is indicated by the geological cross-sections shown in Figs. 2 and 3. These sections show that the formations underlying the property extend from the Lower Silurian lin~estones up to the Devonian slates, including the numbers of the Paleozoic system of rocks as defined by the geological surveys of Virginia, Pennsylvania and New York, from No. 11. to No. VIII. • No. IX. Old Red Sandstone, No. VIII. Slates and Shales, Devoman-

Jan 1, 1900